Halomethyl ethers



Patented Dec. 23, 1941 HALOHETHYL ETHEBS Herman A. Brnlon and Clinton W. MacMnllen, Philadelphia. Pa asslgnorl to Itiihm 8a Haas Company, Philadelphia, Ia. I

No Drawing. Application September 2, 1938,

Serial No. 228,145

7 Claims. (Cl. 260-613) halomethyl substituted aromatic ethers having the general formula (halCHz);--R--XA--Y wherein ha] is a member of the group consisting of chlorine and bromine, n is an integer less than three, R is a carbocyclic aromatic radical, X is a member of the group consisting of O and S, A is an alkylene group, the chain of\which may be interrupted by'a member of the group consisting of O and S, and Y is a member of the group consisting of OI-I, -Oalkyl, -aryl, OCO alkyl, CO-alkyl, C0O-a1kyl,-COOH, and CHzhal.

These halomethyl compounds may be prepared by condensing an ether of the general formula R-X (wherein R and X have the above mentioned significance), with formaldehyde and hydrogen chloride or hydrogen bromide; R having a replaceable nuclear hydrogen atom.

The reaction takes place readily in concentrated hydrochloric or hydrobromic acid solution at temperatures of about 10-60 C. without splitting the ether linkages. The compounds thus obtained may be used in the preparation of wetting agents, resins, insecticides, mothproofing agents, tanning materials, and other industrial products.

Typical ethers which are suitable for the preparation of these new halomethyl compounds are I and compounds containing the radical ROA in which R is an aromatic resldue'which may contain other nuclear substituents sucha's alkyl,

aralkyl, 'cycloalkyl, aryl, nitr'o, halogen; acyl groups. etc. but must be free of radicals or groups which are destroyed by the hydrogen halide or the formaldehyde. Such groups are for example, the amino, diazo, and aldehyde groups. It must also be free of hydroxyl groups which would cause condensation of the formaldehyde in a different manner. These aromatic radicals must have at least one replaceable nuclear hydrogen atom and in case more than one is available, more than one (halCI-I2) group can be introduced into the aromatic radical. The aromatic radical may be mononuclear or polynuclear such as a benzene, naphthalene, phenanthrene, anthracene, or other polynuclear radical.

The reaction is carried out in general by suspending the aryl ether in the aqueous hydrohalogen acid containing the formaldehyde and passing in dry hydrogen halide at temperatures of about 10 to 60 C. The aryl ether may also be dissolved in a suitable non-reactive organic solvent such as petroleum ether, ethylene dichloride, etc. The formaldehyde may be used in the form of an aqueous solution or as paraformaldehyde. The products obtained are usually low-melting solids or thick oils.

This invention may be illustrated by the following examples. It is not limited, however, to the exact conditions of time, temperature, and reagents shown as it may be otherwise practiced within the scope of the appended claims.

Example 1.-A stream of dry hydrogen chloride was passed into a mixture of grams of phenoxyethoxyethyl chloride, 102 grams of 37% formaldehyde, and 300 cc. of concentrated hydrochloric acid for 8 hours at a temperature of about 30 C., the reaction mass being stirred throughout this period. A light brown oil formed which was separated, dissolved in benzene and washed. with ice'water. The benzene solution was dried with anhydrous sodium sulphate, filtered, and the solvent evaporated in vacuo, leaving 116 grams of oil which on cooling changed to a white solid. This material was purified by distillation in vacuo. It boiled at 2'10-215 C./5 mm. and the distillate solidified to a crystalline mass which on recrystallization from petroleum ether was obtained in the form of white crystals having a melting point of 52-54" C. The determination of chlorine content showed it to be di(chloromethyl) phenoxyethoxyethyl chloride having the probable formu- Example 2.A mixture of 156 grams of phenoxyethyl chloride, 500 grams of 30% formaldehyde, and 500 cc. of concentrated hydrochloric acid was heated at 45-55 C. and stirred vigorously while a stream of dry hydrogen chloride was passed in for 8 hours. The semi-solid mate- I rial was purified by washing with cold methyl alcohol. The white crystalline, solid obtained having a melting point of Gil-62 C. was di(chloromethyl) phenoxyethyl chloride having the probable formula:

mango-$11,011.01

HlCl

Example 4.-A mixture of 44 grams of p-chlor- 65 grams of 37% formaldehyde, and 200 cc. of concentrated hydrochloric acid was heated at 50-60 C. and stirred vigorously while a stream of dry hydrogen chloride was passed through the mixture for 10 hours. A brown oil layer seprated which was dissolved 'in benzene, washed, dried, and the solvent removed in vacuo. 50 grams of a clear, brown oil remained which was chloromethyl-phenyl p-chlorethoxyethyl sulphide having the formula Example 5.A mixture of 118 grams of ochlorphenoxy ethoxyethyl chloride, 90 grams of 37% formaldehyde, and 300 cc. of concentrated hydrochloric acid was heated at 50-60 C. and stirred vigorously while a stream of dry hydrogen chloride was passed through the mixture for 18 hours. A brown oil separated which was washed and dried as described above. On evaporation of the solvent a clear light brown oil weighing 126 grams remained. This was chloromethyl o-chlorphenoxyethoxyethyl chloride having the probable formula CiCHQ-O clmo CzH4Cl 1 Example 6.-A mixture of 131 grams of o-secoctyl phenoxy ethoxyethoxyethyl chloride, 60 grams of 37% formaldehyde, and ,300 cc. of concentrated hydrochloric acid was heated at 50-60 C. while a stream of dry hydrogen chloride passed in for about 20 hours. The product was isolated as described above. The light brown oil was o-sec-octyl chloromethyl phenoxyethoxyethoxyethyl chloride having the formula:

CHI(CH2) 5CHCcHr-0 C:H4O 011140 0:11:40]

Ha HzCl In a similar manner lauryl phenoxyethoxyethyl chloride was converted to its chloromethyl derivative which is a pale yellow oil.

Example 7.A mixture of 160 grams of pphenyl phenoxyethoxyethoxyethyl chloride, 142 grams of 37% formaldehyde, and 300 cc. of concentrated hydrochloric acid was heated at fill-60 Crand stirred while a stream of dry hydrogen chloride was passed in for 10 hours.

151gramsofadarkbrownoilwasiso1atedin the usual manner; This product was chloromethyl p-phenyl phenoxyethoxyethoxyethyl chloride.

Example 3.--81.6 grams of p-cyclohexyl phenoxyethoxyethoxyethyl chloride, 41 grams of 37% formaldehyde, and 200 cc. of concentrated hydrochloric acid were heated at 50-60 C. and a stream of dry hydrogen chloride passed in for 11 hours. A clear, dark-green oil weighing 68 grams was isolated as described above. The product obtained was p-cyciohexyl chloromethyl phenoxyethoxyethoxyethyl chloride having the probable formula- CHICKS /GH OCsHrO CrH4O CiHACl CHaCH:

Example 9.83.6 grams of p-benzyl phenoxyethoxyethoxyethyl chloride, 81 grams of 37% formaldehyde, and 200 cc. of concentrated hydrochloric acid were heated at 40-50 C. and a stream of dry halogen chloride passed in for 8 hours. The clear brown oil, separated as described above, was chloromethyl pbenzyl phencxyethoxyethoxyethyl chloride.

Example 10.A mixture of 136.8 grams of lauryl methyl phenoxvethoxyethoxyethyl chloride, 60 grams of 37% formaldehyde, and 300 cc. of concentrated hydrochloric acid was heated at 50 -60 C. and a stream of dry hydrogen chloride passed in for 27 hours. The red brown oil, isolated as described above, was chloromethyl lauryl methyl phenoxyethoxyethoxyethyl chloride having the probable formula Example 11 .A mixture of 156 grams of p-teroctyl phenowethoxyethyl chloride, 30 grams of paraformaldehyde, and grams of ethylene dichloride, was stirred while a stream of dry hydrogen chloride was passed in for 17 hours at about 30 C. A red oil layer separated which was washed with cold water, dried with anhydrous sodium sulphate, filtered, and the ethylene dichloride distilled off in .vacuo. A clear brown oil weighing 137 grams was obtained. The product was p-ter-octyl-chloromethyl phenoxyethoxyethyl chloride having the probable formulatcr-CrHuQO 0111.0 cinlcl moi Example 12.A mixture of 178.4 grams of pter-octyl phenoxyethoxyethoxyethyl chloride, 41 grams of 37% formaldehyde, 300 cc. of concentrated hydrochloric acid, and 12 grams of powdered anhydrous zinc chloride was stirred and cooled at about 0 C. while a stream 'of dry hydrogen chloride posed through the mixture mm a 3 iorabout6hours. Thismixturewaspouredonto drochlcric acid was vigorously stirred while a ice and the product extracted with benzme. stream or dry hydrogen chloride was passed in The benzene solution was washed with ice water, for about 8 hours without heating or cooling.

dried, filtered, and the solvent removed in A veryviscous layer separated which was washed vacuo. The clear pale yellow oil remaining was and dried on a porous plate. The brown elastic chloromethyl p-ter-octyl phenoxyethoxyethoxymass was tetra(chloromethyl) -phenonethoxyethyl chloride. ethoxyethyl sulphide having the probable Example .13.A mixture of 32 grams of oi'orrnuia- ClOBrQ-WOGaHrOflfi-S-GsHrOCzHaOCrHaO-QQM c c: moi

phenyl phenoxy ethanol, 75 grams oi 30% Iorm- Emmple 20.--A mixture oi 104 grams of butyl aldehyde, and 90 cc. of concentrated hydrochloric phenoxy acetate, 90 grams o! 3'! iormaldehyde,

acid was heated at 35-50 C. and a stream oi dry and 300 cc. of concentrated hydrochloric acid hydrogen chloride passed in for '1 hours. The was stirred while a stream of dry hydrogen product was isolated in the usual manner. It chloride was passed in for 7 hours without heatwas an oil which on analysis was formd to be ing or cooling. A yellow layer formed which dl(chloromethyl)o-phenyl phenonethanol. was dissolved in benzene, washed, dried, and 1 Example 14.A mixture oi '76 grams of phenexy the benzene removed in vacuo. A clear yellow oil acetic acid, 90 grams of 37% formaldehyde, and remained which was butyi dichloromethyl phe- 300 cc. of concentrated hydrochloric acid was noxyacetatehaving the probable formulaheated at 50-60 C. and a stream of dry hydrogen as chloride passed in forfit hours. A viscous mass CI-CEQ-QOEGOOGIH' separated which was washed and dried on a porous plate. Analysis showed the product to m be di(chloromethyl) phenoxyacetic acid. 31111111118 mixture 01 87- ams 0! Example 15.A mixture of so ramsorphemxy 3o pheno y h xy l lau ether. 61 grams or ethyl acetate, 90 grams of 37% formaldehyde. 37% f rm y and 200 cc. of concentrated and 300 cc. of concentrated hydrochloric acid was hydrochloric acid was stirred while a stream 01' stirred while a stream of dry hydrogen chloride dry hy r n chloride was pased in without was passed infor 7 hours at -40 C. Aresinous heating ling for 11 hours. The oil layer mass was obtained which was washed and dried which separated was p rified as described above. on a porous plate. Analysis indicated it to be The product was a clear amber oil which was the dichloromethyl derivative of phenol! ethyl dimhlol'omfithyl) -P fl y hyl 1?! acetate. ether having the probable formula- Ezample 16.-A mixture of 46 grams of o-nitro phenoxy ethoxyethyl chloride, 41 grams or 37% C10 cflilocamoculia formaldehyde, and 200 cc. of concentrated hymm drochloric acid was stirred while a stream of dry hydrogen chloride passed in at 30-60 C. The bromo-methyl and di(bromomethyl) defor about 8 hours. A brown oil separated which rivatives of compounds of the above type may be was purified in the usual manner. The product obtained by replacing the hydrogen chloride with obtained was chloromethyl o-nitro phenoxyhydrogen bromide. In some cases the aryl ethoxyethyl chloride having the probable p yalkylene ether halides give resinous prodformulaucts which are diflicult to isolate. o-Methoxy ClCHz-CtHz-O crmo CaHiCl phenoxyethonethyl chloride gave a viscous conte. 5o e analyzing for the diehloromethyl de- EMPWPA mixtureommmsowmtisfiefitififihm' m mfyttlfi hexylphenoxyethoxyethyl n-butyl ether, 51 grams v acid yields a resinous chloromethyl derivafiv of 37% formaldehyde, and 200 cc.of concentrated we claim. hydrochloric acid was stirred while a stream of c n dry hydrogen chloride was passed in at 30-50' C. 55 pounds of the general formula for 7 hours. A clear yellow oil was obtained (ClCH:)-ROACl which was chlormethyl p-cyclohexylphenoxyin which n is an in er less than three ethoxyethyl n-butyl ether having the probable a mmclin and A is z f mrmulam allwiene ether chain.

CsH11CsH3(CI'I2C1) 0C2H4OC3H4OC4H. compolmljs 0 he g n ral formula Example 18.A mixture of 156 grams oi! p-ter- (ClCHzl=RO-AC1 octyl phenoxyethoxye hyl chloride- 30 m of m which 1; is an in or less than three paraformaldehyde, and 150 grams of petroleum phenyl group'and polyauqlene m m ether (B. P. 30-60 C.) was stirred while a stream A compound of the general fo 111a.-

of' dry hydrogen chloride was passed in for 16 hours at 3o-40 c. The turbid brown solufion =OCH=CH=CI was washed with cold water, dried with anhywherein n is an integer less than three and R is drous sodium sulphate, filtered, and the solvent phenyl group, distilled off in vacuo. A brown oil remained 4 A compound of t formula... which was chloromethyl p-ter-octyl phenoxy' ethoxyethy] chlorid (ClCH:)aR-OCH2CH:O

Example 19.A mixture of 26 grams ofphenox. CW yethoxyethoxyethyl sulphide, 41 grams 0! 37% wherein a is an integer less than three and R formaldehyde, and 200 cc. of concentrated hyis a phenyl group.

5. A compound having the formula- '7. Compounds of the formula (had-CH2) .R-x-Ahal CICH o-cmcmocmcmci wherein hal is a. member of the group consisting 5 of chlorine and bromine, n is an integer less than moi three, R is a. carbocyclic aromatic radical, x is a. member of the class consisting of O and S, 6. A compound having the tormuiaand A is an alkylene group, the chain of which may be interrupted by a. member of the class [0 consisting of 0 and S. C1CHr -o-cmcmci HERMAN A. BRUSON. HaCl CLINTON W. MACMULLEN. 

